Catalytic activity accelerant used in petroleum hydrogenation

ABSTRACT

The present invention provides a catalytic activity accelerant. The accelerant is added to stock oil for increasing the catalyst activity, the depth of catalytic hydrogenation and the yield of catalytic hydrogenation product, degrading the reaction conditions of catalytic hydrogenation, and improving the quality of product. The catalytic activity accelerant is consisted of an alkyl succinimide derivative, an alkyl phenol and a surfactant. The amount of the alkyl succinimide derivative in the accelerant is 5-70 wt. %. The amount of the alkyl phenol in the accelerant is 2-70 wt. %. The amount of the surfactant in the accelerant is 2-70 wt. %

FIELD OF THE INVENTION

[0001] The present invention relates to a catalytic activeaccelerant(promoter), which can enhance the catalyst activity, the depthof catalytic hydrogenation and the yield of catalytic hydrogenationproduct in petroleum hydrogenation.

TECHNICAL BACKGROUND

[0002] As an extremely complex system, petroleum comprises not onlyalkanes, cyclic alkanes and aromatic hydrocarbons of different molecularweight, but also a small amount of sulfides, oxides and nitrides, aswell as some trace amounts of metal compounds of iron, copper, nickel,vanadium, etc. In the process of petroleum processing, these hydrocarbonor non-hydrocarbon substances will subject such chemical reactions ascracking, condensing and coking. Now, the catalytic hydrogenationprocess is usually conducted by adding hydrogen into the feedstock oilunder conditions of high temperature and high pressure both at home andabroad. However, with the ever-increasing contradictions between thetrend of heavy crude oil and need to be light for the petroleumproducts, the feedstock oil to the reprocessing device is becomingheavier and inferior in quality, that finally causes some seriousproblems to the catalyst for hydro cracking, hydro desulfurization andcatalytic cracking devices in many refineries and petrochemical plantssuch as coking, scaling and eventually deactivated, even influencing thecatalytic bed of hydro refining and hydro cracking to fasten pressuredecline, thus seriously affecting and confining the action cycle andstable operation of the devices.

[0003] The problem of catalyst deactivation is obvious especially in thehydro cracking device because of its high reacti n pressure of 15-20MPa, high temperature of 380-420C° and the one-lot filling of catalystof 500-1000 tons. In some cases, the equipment has to be stopped tomaintain only after 3 to 5 months' operation due to catalystdeactivation. Thus, it is an urgent task to prevent or alleviate thecatalyst deactivation and enhance catalyst efficiency in hydro crackerto lengthen the action cycle to acquire more economic benefits.

[0004] The catalysts used in the process of petroleum hydrogenation areinorganic, while the feedstock involved in the hydrogenation reactionare organic materials and non-polar hydrogen. Accordingly, thecontacting activity of feedstock with catalyst is relatively poor, andcoke easily formed on the surface of the catalyst will affect activityof the catalyst.

[0005] There have been quite a few reports both at home and abroad onstudy of new hydrogenation catalysts in recent years. However, none ofthem addresses to the addition of catalytic active accelerant to thefeedstock oil during the hydrogenation to improve the catalyst activity,the depth of catalytic hydrogenation and the yield of catalytichydrogenation products, and weaken the reaction conditions of catalytichydrogenation. It would be a tremendous contribution to theinternational catalytic hydrogenation techniques that catalytic activeaccelerant is applied in practical production to increase the catalystactivity and prolong the service life of the catalyst.

DISCLOSURE OF THE INVENTION

[0006] The objective of the present invention is to increase thecatalyst activity, the depth of catalytic hydrogenation and th yield ofcatalytic hydrogenation product, weaken the reaction conditions ofcatalytic hydrogenation, and improve the quality of product by adding acatalytic active accelerant into the fe dstock oil, in the course ofcatalytic hydrogenation of the p troleum processing.

[0007] The objective can be achieved by the following measures:

[0008] The catalytic active accelerant of the present invention iscomposed of alkylsuccinimide derivative, alkylphenol and surfactant.

[0009] The alkylsuccinimide derivatives used in the present inventionhave the following structural formula:

[0010] wherein

[0011] R1 to R16 are H or alkyl, n refers to degree of polymerization ofCH2CH2N and is a number of 1 to 8.

[0012] Either pure or mixted alkylsuccinimide derivatives can be usedwhen making the accelerant, and its percentage by weight in theaccelerant is in the range of 5 to 70%, and preferably 10 to 50%.

[0013] Th alkylphenols used in the present invention can be the mono- orpoly-phenol or naphthol derivatives with its structural formula, forexamples, as f llows:

[0014] wherein

[0015] R₁ to R₆ can be H, OH or alkyl and alkenyl having 1 to 10 carbonatoms.

[0016] Either pure or mixed alkylphenols can be used in the accelerant,and its percentage by weight in the accelerant is in the range of 2 to70%, and preferably 5 to 40%.

[0017] The surfactants used in the accelerant of the present inventioncan be pure or mixed esters non-ionic surfactant produced by reactingthe following polyhydric alcohols with fat acids. The polyhydricalcohols can be propanediol, propanetriol, pentaerythritol,cyclohexanepolyols, sorbitol, diethylene glycol, triethylene glycol andmannitol or their mixture. The fat acids can be either saturated orunsaturated fat acids having 6 to 22 carbon atoms.

[0018] The C₁-C₂₆ alkyl sulfonate anionic surfactants can also be usedin the accelerant of the present invention.

[0019] The percentage by weight of surfactants added to the accelerantis in the range of 2 to 70%, and preferably 7 to 40%.

[0020] Solvents used in the accelerant of the present invention arehydrocarbon solvents, which include benzene, toluene, xylene, gasoline,diesel oil, kerosene, petroleum ether, naphtha and cyclic alkane.

EXAMPLES

[0021] The catalytic active accelerant of the present invention can bemade from alkylsuccinimide derivatives, alkylphenols, and surfactantsmentioned above by adding an alkylphenol to an hydrocarbon solvent toform a solution, followed by adding an alkylsuccinimide derivative and asurfactant to said solution, and heating and mixing the mixture at thetemperature of 30 to 100C° by conventional method. For specificoperations, see Table 1. TABLE 1 The composition of the catalytic activeaccelerant Name of accelerant alkylsuccinimide derivative alkylphenolsurfactant HCA-1

Weight 15% 20% 30% Percentage HCA-2

Weight 40% 35% 15% Percentage HCA-3

Weight 30% 20% 30% Percentage HCA-4

Weight 20% 20% 40% Percentage HCA-5

Weight 20% 15% 50% Percentage HCA-6

(C₁₂H₂₅SO₃)₂Ca Weight 30% 15% 30% Percentage

[0022] Th reaction conditions for accelerant HCA-1 in Table 1 are: 60C°for reaction temperature, diesel oil as solvent, 35% of weightpercentage.

[0023] The reaction conditions for accelerant HCA-2 in Table 1 are: 70C°for reaction temperature, gasoline as solvent, 10% of weight percentage.

[0024] The reaction conditions for accelerant HCA-3 in Table 1 are: 50C°for reaction temperature, toluene as solvent, 20% of weight percentage.

[0025] The reaction conditions for accelerant HCA-4 in Table 1 are: 90C°for reaction temperature, benzene as solvent, 20% of weight percentage.

[0026] The reaction conditions in accelerant HCA-5 in Table 1 are: 80C°for reaction temperature, kerosene as solvent, 15% of weight percentage.

[0027] The reaction conditions in accelerant HCA-6 in Table 1 are: 40C°for reaction temperature, diesel oil as solvent, 25% of weightpercentage.

[0028] The efficiency of the catalytic active accelerants according tothe present invention was evaluated using dynamic evaluation device forcatalytic hydrogenation. The process conditions of evaluation are:concentration of the catalytic active accelerant added of 30 to 200 ppm,operation pressure of 12 to 16 MPa, reaction temperature range of 370 to400C°, space velocity of 0.7 to 1.5 h⁻¹, ratio of hydrogen to oil of 800to 1000, testing time of 500 hrs. Specific data were shown in Table 2and Table 3.

[0029] Table 2: Comparison of operation efficiency with/withoutcatalytic activ accelerant (pressure of 14 MPa and space velocity of 1.0h¹) TABLE 2 Comparison of operation efficiency with/without catalyticactiv accelerant (pressure of 14 MPa and space velocity of 1.0 h⁻¹)Gasoline yield Diesel oil yield Total yield (%) (%) (%) With No With NoWith No Yield Accel- Accel- addit- Accel- addit- Accel- addit- increaseerant erant ion erant ion erant ion (%) HCA-1 26.7 15.6 38.5 27.8 65.243.4 21.8 HCA-2 19.8 15.4 36.6 27.3 56.4 42.7 13.7 HCA-3 32.6 14.9 34.228.4 66.8 42.4 24.4 HCA-4 28.3 15.0 32.7 28.0 61.0 43.0 18 HCA-5 31.215.5 35.4 27.6 66.6 43.1 23.5 HCA-6 36.9 14.7 30.5 28.2 67.4 42.9 24.5

[0030] TABLE 3 Comparison of oil quality (HCA-4,100 ppm) With AccelerantNo Gasoline (m %) addition Total alkanes 59.535 48.425 Total cyclic28.628 34.927 alkanes Total aromatic 11.207 15.670 hydrocarbon Sulfur(ppm) 9.1 180 Nitrogen (ppm) 0.2 0.9 With No Diesel oil Accelerantaddition Saturated 92.50 89.29 hydrocarbon (m %) Monocyclic 7.50 10.71hydrocarbon (m %) Sulfur (ppm) <30 <30 With No Tail oil Accelerantaddition Saturated 99.20 96.180 hydrocarbon, m % Monocyclic 0.80 3.82hydrocarbon, m % Sulfur (ppm) <40 <40

[0031] As indicated in the above data, the yield of light oil wasremarkably increased by addition of catalytic active accelerant. Thenaphtha, of which the total aromatic hydrocarbon comprises about 11%,the total sulfur content is less that 10 ppm, and the total nitrogencontent is less than 0.2 ppm, obtained in this way will provideexcellent cracking feedstock to produce ethylene and raw material forhydrogen, or ammonia production. The diesel oil, in which saturatedhydrocarbon accounts for about 92.5%, monocyclic aromatic hydrocarbon7.5%, and the total sulfur content is less than 30 ppm, obtained in thisway is high quality diesel and additional component of high cetane. Itis a new “green fuel”. The tail oil obtained in this way provides goodFCC or hydro cracking raw materials since its saturated hydrocarboncontent accounts for about 99%. The total yield increase about 20%.

[0032] The new catalytic active accelerant developed by the inventorstakes the advantage of its activity to improve the contact ability ofhydrogen, and petroleum with catalyst. The catalyst will maintain highlyactive state for a long time since its surface is infiltrated andcleaned by the accelerant. The results of dynamic contrast pilot tests(with or without adding accelerant to th f dst ck oil) show that th tmperature of catalytic bed can be increased by 1˜10C° and th gross yi Idof gasoline and diesel oil will b increased by 2˜25% under th operationconditions of: th conc ntration of th accelerant in the feedstock oilbeing in the range of 30 to 200 ppm, operation pressure ranging from 12to 16 MPa, reaction temperature being in the range of 370 to 400C°,space velocity being in the range of 0.7 to 1.5 h⁻¹, and ratio ofhydrogen to oil being from 800 to 1000. As a result, not only thecatalyst activity is improved, and its service life is prolonged, alsothe operation conditions for catalyzed hydrogenation are weakened. Theapplication of this new accelerant is of tremendous practicalsignificance in improvement of the output of the equipment and reductionof consumption.

What is claimed is:
 1. A catalytic active accelerant used in petroleumhydrogenation, characterized in that the catalytic active accelerant iscomposed of an alkylsuccinimide derivative, an alkylphenol, and asurfactant, wherein alkylsuccinimide derivative comprises 5 to 70%,alkylphenol 2-70%, and surfactant 2-70% by weight based on the totalweight of the catalytic active accelerant.
 2. The catalytic activeaccelerant used in petroleum hydrogenation according to claim 1, whereinthe alkylsuccinimide derivatives used in the form of the pure or mixturein the present invention have the following structural formulae:

wherein R1 to R16 are H or alkyl, n refers to degr e of polymerizationof CH2CH2N, and is a number of from 1 to
 8. 3. The catalytic activaccelerant used in petroleum hydrogenation according to claim 1 or claim2, wherein the preferable percentage by weight of alkylsuccinimidederivative added in the accelerant is in the range of 10 to 50%.
 4. Thecatalytic active accelerant used in petroleum hydrogenation according toclaim 1, wherein the alkylphenol can be the pure or mixture of the mono-or poly-phenol or naphthol derivatives with its structural formulae asfollows:

wherein R₁ to R₆ are H or the alkyl and alkenyl having 1 to 10 carbonatoms.
 5. The catalytic active accelerant used in petroleumhydrogenation according to claim 1 or claim 4, wherein the preferablepercentage by weight of alkylphenol added in the accelerant is in therange of from 5 to 40%.
 6. The catalytic active accelerant used inpetroleum hydrogenation according to claim 1, wherein the surfactantused in the accelerant of the present invention is pure or mixed estersnon-ionic surfactant produced by reacting polyhydric alcohols with fatacids.
 7. Th catalytic active accelerant used in petroleum hydrogenationaccording to claim 6, wherein the polyhydric alcohols are propanediol,propanetriol, pentaerythritol, cyclohexanepolyols, sorbitol, diethyleneglycol, triethylene glycol, or mannitol.
 8. The catalytic activeaccelerant used in petroleum hydrogenation according to claim 6, whereinthe fat acids are either saturated or unsaturated fat acids having 6 to22 carbon atoms.
 9. The catalytic active accelerant used in petroleumhydrogenation according to claim 1, wherein the surfactant used in theaccelerant of the present invention is anionic surfactant of C₁-C₂₆alkyl sulfonate.
 10. The catalytic active accelerant used in petroleumhydrogenation according to claim 1, 6 or 9, wherein the preferablepercentage by weight of surfactant added in the accelerant is in therange of 7 to 40%.
 11. The catalytic active accelerant used in petroleumhydrogenation according to claim 1, wherein solvents used in thecatalytic active accelerant of the present invention are hydrocarbonsolvents.
 12. The catalytic active accelerant used in petroleumhydrogenation according to claim 1 or 11, wherein the hydrocarbonsolvents used in the catalytic active accelerant of the presentinvention are benzene, toluene, xylene, gasoline, diesel oil, kerosene,petroleum ether, naphtha or cycloalkanes. and is a number of from 1 t 8.3. The catalytic active accelerant used in petroleum hydrogenationaccording to claim 1 or claim 2, wherein the preferable percentage byweight of alkylsuccinimide derivative added in the accelerant is in therange of 10 to 50%.
 4. The catalytic active accelerant used in petroleumhydrogenation according to claim 1, wherein the alkylphenol can be thepure or mixture of the mono- or poly-phenol or naphthol derivatives withits structural formulae as follows:

wherein R₁ to R₆ are H, OH or the alkyl and alkenyl having 1 to 10carbon atoms.
 5. The catalytic active accelerant used in petroleumhydrogenation according to claim 1 or claim 4, wherein the preferablepercentage by weight of alkylphenol added in the accelerant is in therange of from 5 to 40%.
 6. The catalytic active accelerant used inpetroleum hydrogenation according to claim 1, wherein the surfactantused in the accelerant of the present invention is pure or mixed estersnon-ionic surfactant produced by reacting polyhydric alcohols with fatacids.
 7. Th catalytic active accelerant used in p troleum hydrogenationacc rding to claim 6, wh rein the polyhydri alcohols are propanediol,propanetriol,